Penetrating oil composition

ABSTRACT

Penetrating-oil compositions are prepared in which a mineral base oil having a viscosity between about 140 and 600 S.U.S. at 100* F. is compounded with ingredients tending to impart penetrating properties, rust inhibition and rust-dissolving properties thereto. The base oil may be blended, if desired, with a mineral distillate solvent oil, with between about 3 and about 25 percent of a rust preventive, which is a mixture of alkali metal petroleum sulfonates and carboxylic acids obtained by the oxidation of paraffin wax, and with between about 0.5 and about 25.0 percent of the mono or diesters or mixed mono and diesters of phosphoric acid and a long chain fatty alcohol in which the aliphatic chain of the alcohol contains a minimum of nine carbon atoms per molecule and wherein, before the reaction of the alcohol with the phosphoric acid, from 1 to 6 moles of an alkylene oxide of two or three carbon atoms per molecule is reacted with each mole of the alcohol. The final blended penetrating-oil composition has a viscosity of between about 50 and 200 S.U.S. at 100* F.

United States Patent Warren C. Pattenden; Robert E. Emond, both of Mooretown,

[721 Inventors Nov. 30, 1971 Esso Research and Engineering Company ,[45] Patented [73] Assignee [54] PENETRATING OIL COMPOSITION 9 Claims, No Drawings [52] U.S. C1 252/33.4, 252/49.8, 252/389 [51] lnt.Cl Clm1/40 [50] Field of Search 252/33.4, 49.8, 389

[ 5 6 References Cited UNITED STATES PATENTS 2,448,093 8/1948 Gittings 252/59 2,467,176 4/1949 Zimmer et al. 252/33.4

2,632,694 3/1953 Watkins 252/33.4 2,672,444 3/1954 Wasson et al.. 252/49.8 3,033,889 5/1962 Chiddix et al.. 252/49.8 3.180829 4/1965 Cobb et a1. 252/33.4

Assistant Examiner-l. Vaughn Allomeyslearlman and Stahl and Ernest V. Haines ABSTRACT: Penetrating-oil compositions are prepared in which a mineral base oil having a viscosity between about 140 and 600 S.U.S. at 100 F. is compounded with ingredients tending to impart penetrating properties, rust inhibition and rust-dissolving properties thereto. The base oil may be blended, if desired, with a mineral distillate solvent oil, with between about 3 and about percent of a rust preventive, which is a mixture of alkali metal petroleum sulfonates and carboxylic acids obtained by the oxidation of paraffin wax, and with between about 05 and about 25.0 percent of the mono or diesters or mixed mono and diesters of phosphoric acid and a long chain fatty alcohol in which the aliphatic chain of the alcohol contains a minimum of nine carbon atoms per molecule and wherein, before the reaction of the alcohol with the phosphoric acid, from 1 to 6 moles of an alkylene oxide of two or three carbon atoms per molecule is reacted with each mole of the alcohol. The final blended penetrating-oil composition has a viscosity of between about and 200 S.U.S. at F.

PENETRATING OIL COMPOSITION DESCRIPTION OF THE INVENTION The present invention relates to the compounding of a novel penetrating oil composition having unique properties. In many instances threaded nuts on bolts freeze and threads of machine screws and similar parts made of iron steel or alloys containing iron have marked tendency to oxidize or rust. Particularly so where such threaded components are subjected to conditions of high temperature or corrosive atmospheres such as acidic gases, sea water or other corrosive atmospheric and surrounding gases, for example, in the case of heat exchangers whose heads are bolted and which are constantly under hightemperature conditions, it becomes necessary for maintenance purposes to remove the heads for the purpose of cleaning the tubes. Oftentimes the threaded bolts by which the heads are secured by means of tightened nuts have corroded to the point that it is a practical impossibility to unscrew the nuts from the bolts because of excessive corrosion conditions which have built up since the last maintenance operations performed on those heat exchangers. In such instances, it is necessary to chisel or cut the nuts or heads from the bolts in order to complete the maintenance operations and even in those instances where this is not done the application of high torque forces to the nuts will only result in the fracturing of the bolts rather than in the loosening and unscrewing of the nuts securing those bolts.

For this reason, frozen nuts and bolts and the removal of such nuts from such bolts where atmospheric rusting has developed on these parts constitute a large problem in petroleum-refining operations and in chemical plant operations, so much so that there is a ready and large market for penetrating oils which can and do successfully eliminate the seizure conditions at least to unscrew the nuts from such seized bolts without damage either to the nuts or the bolts.

In the past, oils of low viscosity, which are usually specially compounded oils and which are of high penetrating power, i.e., which have extremely low surface tension properties, have been applied in such instances for the purpose of unfreezing or freeing the threads of the bolts so that the nuts, with a moderate amount of torque force applied thereto, may be readily unscrewed therefrom. This freezing due to corrosion and rusting is particularly troublesome in those instances where the tightened bolts are subjected to high degrees of heat and/or to corrosive atmospheric conditions.

It has now been found that a four-component penetrating oil composition is unexpectedly useful when applied to highly corroded or frozen nuts on threaded bolts for the purpose of loosening or freeing the frozen sliding parts which are, of course, screw threads. The novel composition not only is in itself a good rust preventive when applied to the screw threads at the time such nuts and bolts are put in place and in use but, surprisingly enough, it has been found that the specific fourcomponent penetrating oil composition has the additional property of being able to actually dissolve the rust particles from the parts so treated. So far as known, no penetrating-oil composition heretofore compounded and used for these types of operations has the ability to actually dissolve iron rust coatings and particles.

A number of patents have been issued in which penetrating oil compositions have been compounded; typical of these patents are Zimmer et al., U.S. Pat. No. 2,467,l78, patented Apr. 12, I949 Bartlett et al., U.S. Pat. No. 2,758,088, patented Aug. 7, 1956; and Cobb et al., U.S. Pat. No. 3,180,820, patented Apr. 27, 1965. In each of these instances, the patents have disclosed attempts to solve this problem by the expedient of oiliness agents, rust preventive action, and reduction of surface tension properties, i.e., an ability to spread over a wide area and to penetrate small crevices. So far as can be determined from a study of these solutions to the problem, no one has discovered any reagent which does, in fact, dissolve the iron rust which is always present under such corrosive and/or high-temperature conditions. The instant novel composition has unexpectedly and unobviously, in a four-component penetrating oil composition, attained the ability to dissolve iron rust, so that a positive desirable property is present in this novel composition. The four-component composition embodies a low or medium cold test petroleum oil base as the major component of the composition plus three other components; a paraffinic solvent oil for the lowering of viscosity, a rust-preventive material, and finally, a material which acts as a cosolvent for the rust-preventive composition as well as being an iron rust dissolver and a rust inhibitor. The last three components are generally employed in lesser amounts, individually, than is the amount of base mineral oil employed although it is not necessary that such be the case, except as a practical matter. The final four-component blended penetrating oil composition has a viscosity of between about 50 and about 200 S.U.S. (Saybolt universal seconds) at F. It has been found, thus, that the surface tension properties are sufi'iciently low, that there is excellent penetrating power of the final composition if the viscosity is within this range. In other words, a highly refined lubricating oil of as much as 600 S.U.S. at 100 F. may be used as the base, if sufficient mineral solvent, mineral spirits, or mixtures of the two are employed to lower the viscosity of the final composition to the aforementioned viscosity range. The petroleum oil base may have an SAE grade of from 10 or 20 to 30. It may have a boiling range of from 600 to as high as l,000 F., and a viscosity between about and 600 S.U.S. at 100 F.. It may be a suitable fraction of paraffinic, asphaltic, naphthenic or mixed crude origin. It is generally a highly refined oil which has been subjected to phenol extraction, solvent dewaxing and hydrofining. Such an oil is generally designated as either a low or medium cold test lubricating oil. One specific, particularly desirable, oil is a Mid-Continent solvent extracted, solvent dewaxed and hydrofined lubricating oil having a viscosity of I60 S.U.S. at 100 F. and a viscosity index of about 90. It is present in the final four-component penetrating oil composition in an amount ranging between about 50 and about 85 percent. As used herein, all percentages are on the basis of weight percent. Any highly refined mineral oil may be employed so long as it possesses the required characteristics, as above defined. The petroleum oil base is hereinafter designated as component A.

Component B of the penetrating oil composition is an aliphatic paraffin solvent distillate oil which may be a solvent naphtha, mineral spirits, varnish makers and painters naphtha (VM&P), a kerosene or a mixture of two or more of these materials. This component is used in a sufficient amount, between about 10 and about 25 percent, to materially lower the viscosity of the final composition so that a marked penetrating effect is present in the final composition. Preferably, between about l5 and about 20 percent mineral spirits having a boiling range between 300 and 450 F. is used. VM&P naphtha between about 200 and about 350 and kerosene between about 325 and about 550 F. are also useful. Optionally, a portion of the solvent oil up to one-half of the total amount may be substituted, by the use of other organic solvents such as butyl cellosolve or the chlorinated aliphatic hydrocarbon solvents, such as ethylene dichloride, trichlorethylene, tetrachlorethylene and the like. Generally, if between about 2 and about 10 percent based on the total composition of these auxiliary solvents are employed, the amount of paraffin solvent oil previously set forth is reduced by like amount. Thus, for example, if about l0 percent of trichlorethylene or tetrachlorethylene is employed in the final composition, the amount of paraffin solvent oil employed would be between about 5 and about l5 percent.

Component C is a rust preventive which is conventionally manufactured and marketed and is generally described as a mixture of a sodium petroleum sulfonate and oxidized hydrocarbon wax (paraffin), the oxidation having been car; ried to a sufficient extent so that carboxylic acids are produced. The sodium petroleum sulfonate component makes up between about 10 and about 25 weight percent while the balance is oxidized wax. The oxidized was has an acid number of about 40-60 and the mixture contains the free carboxylic acid derived from the oxidized wax.

Other conventional rust-inhibiting compounds of these types that may be used are the following: alkaline earth metals, i.e., calcium, barium, or lead petroleum sulfonates or alkaryl sulfonates admixed with acids of oxidized wax. The basic metal hydrocarbon sulfonates are either of petroleum origin (mahogany acids) or of the synthetic type, long chain alkyl substituted benzene type, such as dodecyl benzene sulfonate. These rust-inhibiting or preventive materials are used in amounts ranging between about 3 and about 25 percent of the total composition preferably in amounts of between about 4 and about percent. They are particularly difficult to put into solution in the base oil either alone or in combination with the organic solvent distillates. While it is possible to get as much as 2-3 percent of such rust inhibitors into solution in an admixture of components A and B, best results in the final four-component composition have been secured ifa minimum of at least 5 percent of the total composition constitutes such rust inhibitors. To achieve this amount or a greater amount, in solution, the use ofa cosolvent is necessary.

Component D is fortuitously not only a cosolvent for component C but it is a component which has rust-inhibiting properties, as well. Surprisingly, it has been found also to be a solvent for iron oxide or iron rust. This class of compound is well known and is commercially marketed. Essentially, these rustdissolving and cosolvent compounds are prepared by initially reacting a long chain aliphatic monohydric alcohol with from I to 6 moles ofa C;,C alkylene oxide to alkoxylate the same, followed by the reaction of the alkoxylated alcohol with phosphoric acid to form either the mono or diester or a mixture of the monoand diesters of phosphoric acid. The monohydric aliphatic alcohols, which are generally referred to as the fatty alcohols, must contain a minimum of l2 carbon atoms per molecule, but may contain up to 24 carbon atoms per molecule, in order to achieve their effective cosolvent and rust-dissolving properties. Suitable useful long chain alkyl alcohols are lauryl alcohol, stearyl alcohol, cetyl alcohol, oleyl alcohol or mixed alcohols such as lorol alcohol, palm kernel derived alcohols, coconut nut derived alcohols and the like. In general, ethylene oxide is employed as the alkoxylating agent although propylene oxide is also useful for this purpose. In general, from I to 6 moles of the alkylene oxide is employed per mole of monohydric alcohol. A suitable compound, which is high in efficacy, is prepared specifically by reacting 4 moles of ethylene oxide with 1 mole of oleyl alcohol and subsequently esterifying these with l mole of phosphoric acid. Component C, without the use of component D, cannot be dissolved in a mixture of components A and B if more than 2 or 3 percent, based on the total composition, of component C is added. Although slight heating may be employed to effect a solution oflarger amounts, as soon as the blend is cooled to atmospheric temperature, precipitation of some of component C inevitably results. This is undesirable from the standpoint of practical application and use in a penetrating-oil composition.

in order to test the rust-solubilizing properties of the afore mentioned four-component penetrating oil composition a modified ASTM D665-60 Rust Test was carried out. Steel specimen pins, as described in that test, were weighed and were immersed in a composition comprising 90 percent of a mild cold test highly refined parafi'in oil of I60 S.U.S. at 100 F. and I0 percent salt water mixture for 72 hours at l40 F. At the end of this period the amount of rust formed was determined by reweighing each pin. Thereafter the hereinafter stated quantity of rust solvent (component D) was added to the component A in the salt water mixture. In each of these beakers used, three different amounts of component D were added. At the end of 24 hours ofimmersion. 70 percent of the rust was removed by the use of 3 percent of component D and roughly 85 to 99 percent of the rust was removed by the use of IO percent and percent respectively of component D in the same length of time. The rust appeared initially as discrete particles in the oil mixture but within a short period of time dissolved completely in these oil mixtures whereas in the case of the use of the mild cold test oil alone, without any component D added, the rust did not dissolve and the rust which was removed from the pins remained as dark rust particles of about Az-inch diameter average in the oil. The particle component D used in these comparative runs was the oleyl alcohol alkoxylated mixed monoand diphosphoric esters wherein ethylene oxide originally was reacted with the oleyl alcohol to the extent of about 4 moles of ethylene oxide per mole of alcohol. Only about 3 percent of the rust was removed from the rusted specimens at the end of 24 hours in the case of the base oil used without any component D being added A further test was carried out as follows:

A penetrating oil composition was prepared with the following composition:

Component A Component B Component C Component D Component 8-! Minor amounts, 0.5 percent or less of oleic acid, Aerosol O.T. (a commercial wetting agent), and a conventional antioxidant, were also present. The product has a viscosity of 55 S.U.S. at 100 F. The foregoing composition was evaluated in the following manner:

A number of rusted bolts having nuts screwed thereon (5X%inch) were obtained from a refinery heat exchanger unit. These bolts were so thoroughly rusted that it was necessary that the heads be cut off to permit removal of the bolt. The three bolt heads (nuts) were each treated with about 5 cc. of the foregoing composition and three such other nuts were treated with the same composition but without additive D being present. Still other bolts remained untreated for control purposes. Two hours after applying the oil compositions to the nuts a torque wrench was used to measure the force required to remove the nuts from the bolt stems. An average of the three bolts in each sample was arrived at for the torque reading in ft.-lbs. The untreated nuts gave a torque reading to remove the nuts of about 50 ft.-lbs. The penetrating oil containing no component D gave a torque reading of about 30 ft.- lbs., and the torque reading for the nuts treated with the foregoing composition containing component D in an amount of about l0 percent gave a torque reading of about 8 ft.-lbs.

Still another composition which was employed with success by petroleum refinery maintenance crews in the removal of rust on nuts of bolts in use was the following:

Com onent A Component B Component 8-] Component D The results obtained when applying to rusted-on nuts for about 2 hours proved to be extremely effective and craft maintenance men requested additional quantities of the product for practical and continued use.

Having now thus fully described and illustrated the invention, what is desired to be secured by Letters patent ls:

I. A penetrating-oil composition comprising:

a. from about 50 to about weight percent of a refined mineral base oil having a viscosity at F. of between about and about 600 S.U.S.;

b. from about l0 to about 25 weight percent of a paraffinic distillate solvent oil;

. from about 3 to about 25 weight percent of a mixture of a metal hydrocarbon sulfonate and aliphatic carboxylic acids of oxidized hydrocarbon wax, having an acid number of about 40 to 60, the proportion of sulfonate to wax acids being from about one-ninth to about onefourth; and

d. from about 0.5 to about 25 weight percent of a phosphate ester selected from the group consisting of a monoester, a diester, and mixtures thereof, of phosphoric acid with an alkoxylated long chain aliphatic alcohol wherein the aliphatic radical contains at least 12 carbon atoms per molecule and the alkoxylating is carried out using from 1 to 6 moles of a C to C alkylene oxide per mole of alcohol;

and weight percents being based on the entire composition;

said blended penetrating oil composition having a viscosity at 100 F. of between about 50 and about 200 S.U.S.

2. A penetrating-oil composition as in claim 1 wherein the blended composition contains between about and about 25 percent of component (B) between about and about percent of component (C), and between about 4 and about 10 percent of component (D), the balance being base oil component (A).

J. A penetrating-oil composition as in claim 1 wherein from about I to about 10 percent of the total composition is a chlorinated aliphatic hydrocarbon solvent.

4. A penetrating-oil composition as in claim 1 wherein component (B) has a boiling range between about 200 and about 500 F.

S. A penetrating-oil composition as in claim 1 wherein component (C) is a mixture of alkali metal and alkaline earth metal hydrocarbon sulfonates and oxidized paraffin wax carboxylic acids.

6. A penetrating-oil composition as in claim 1 wherein component (D) is a mixed monoand diester of phosphoric acid reacted with the ethylene oxide reaction product of oleyl alcohol.

7. A penetrating-oil composition as in claim 1 wherein component (D) is a mixed monoand diester of phosphoric acid reacted with the ethylene oxide reaction product of the mixed alcohols derived from coconut oil.

8. A penetrating-oil composition as in claim 1 wherein component (B) is a parafim solvent oil boiling between about 200 and about 350 F. present in the amount of about 17 percent, component (C) is a mixture of sodium petroleum sulfonate and carboxylic acids derived from the oxidation of paraffin wax, present in the amount of about 5.0 percent, and component (D) is an ethoxylated derivative of oleyl alcohol mixed monoand diesters of phosphoric acid, present in the amount of about 10.0 percent, the balance of the composition being a highly refined paraffinic base distillate oil of about I60 S.U.S. at lOO F. and having a viscosity index of about 90.

9. The penetrating-oil composition as in claim 3 wherein component (D) is kerosene present in an amount of about 25.0 percent, together with triclorethylene, present in an amount of about 4.5 percent, component (C) is a mixture of sodium petroleum sulfonate and carboxylic acids derived from the oxidation of paraffin wax, present in the amount of about 5 percent, and component (D) is the mixed monoand diesters of phosphoric acid reacted with the ethoxylated derivative of oleyl alcohol, present in the amount ofabout 10.0 percent, the balance being a highly refined paraffinic distillate oil of about S.U.S. at lOO F. and having a viscosity index of about 90. 

2. A penetrating-oil composition as in claim 1 wherein the blended composition contains between about 10 and about 25 percent of component (B) between about 15 and about 20 percent of component (C), and between about 4 and about 10 percent of component (D), the balance being base oil component (A).
 3. A penetrating-oil composition as in claim 1 wherein from about 1 to about 10 percent of the total composition is a chlorinated aliphatic hydrocarbon solvent.
 4. A penetrating-oil composition as in claim 1 wherein component (B) has a boiling range between about 200* and about 500* F.
 5. A penetrating-oil composition as in claim 1 wherein component (C) is a mixture of alkali metal and alkaline earth metal hydrocarbon sulfonates and oxidized paraffin wax carboxylic acids.
 6. A penetrating-oil composition as in claim 1 wherein component (D) is a mixed mono- and diester of phosphoric acid reacted with the ethylene oxide reaction product of oleyl alcohol.
 7. A penetrating-oil composition as in claim 1 wherein component (D) is a mixed mono- and diester of phosphoric acid reacted with the ethylene oxide reaction product of the mixed alcohols derived from coconut oil.
 8. A penetrating-oil composition as in claim 1 wherein component (B) is a paraffin solvent oil boiling between about 200* and about 350* F. present in the amount of about 17 percent, component (C) is a mixture of sodium petroleum sulfonate and carboxylic acids derived from the oxidation of paraffin wax, present in the amount of about 5.0 percent, and component (D) is an ethoxylated derivative of oleyl alcohol mixed mono- and diesters of phosphoric acid, present in the amount of about 10.0 percent, the balance of the composition being a highly refined paraffinic base distillate oil of about 160 S.U.S. at 100* F. and having a viscosity index of about
 90. 9. The penetrating-oil composition as in claim 3 wherein component (B) is kerosene present in an amount of about 25.0 percent, together with triclorethylene, present in an amount of about 4.5 percent, component (C) is a mixture of sodium petroleum sulfonate and carboxylic acids derived from the oxidation of paraffin wax, present in the amount of about 5 percent, and component (D) is the mixed mono- and diesters of phosphoric acid reacted with the ethoxylated derivative of oleyl alcohol, present in the amount of about 10.0 percent, the balance being a highly refined paraffinic distillate oil of about 160 S.U.S. at 100* F. and having a viscosity index of about
 90. 